Fluorine-containing chiral smectic liquid crystals

ABSTRACT

Compounds are provided which comprise a fluorocarbon terminal portion and a chiral hydrocarbon terminal portion, said terminal portions being connected by a central core, said compounds having tilted smectic mesophases or having latent tilted smectic mesophases which develop when said compounds having said latent mesophases are in admixture with said compounds having tilted smectic mesophases or said compounds having latent tilted smectic mesophases.

This is a division of application Ser. No. 07/373,898 filed Jun. 29,1989, abandoned, which is a division of application Ser. No. 07/053,551filed May 29, 1987, now U.S. Pat. No. 4,886,619, which is acontinuation-in-part of application Ser. No. 06/879,988, filed Jun. 30,1986, now abandoned.

FIELD OF THE INVENTION

This invention relates to chiral smectic liquid crystal compounds whichare optically active and exhibit ferroelectric behavior. Such compoundsare particularly useful in surface-stabilized ferroelectric liquidcrystal display devices.

BACKGROUND OF THE INVENTION

A recent advance in the liquid crystal art has been the utilization oftilted chiral smectic materials in a surface-stabilized device geometryto give very high speed bistable switching not found in devices usingnematic liquid crystals. U.S. Pat. No. 4,367,924 (Clark et al.)discloses the use of chiral smectic C or chiral smectic H liquid crystalmaterials in a device with response times of 1000 to 10,000 times fasterthan previously attained with other liquid crystalline compounds. Clarket al. describe the use of two ferroelectric, i.e., tilted, chiralsmectic, liquid crystal compounds:(+)-p-[n-decyloxy-benzylidenel-p'-amino-(2-methylbutyl)cinnamate(DOBAMBC) and(+)-p-[n-hexyloxy-benzylidenel-p'-amino-(2-chloropropyl)cinnamate(HOBACPC). These compounds have a number of shortcomings includingchemical instability and UV sensitivity. Their inherent short pitchlength and high birefringence severely restrict the design parameters ofthe display devices and their high transition temperatures require theuse of thermal management techniques.

In Ferroelectrics, Vol. 58, p. 3-7, 1984, Keller describes phenylbenzoate ester liquid crystal materials, where one of the alkyl groupsattached to a phenyl ring is optically active, i.e., chiral. Some ofthese materials possess a chiral smectic C mesophase and showferroelectric behavior. Of the compounds that are ferroelectric liquidcrystals, however, most also show an undesired cholesteric mesophase andthose that do not show the cholesteric mesophase have very narrowferroelectric temperature ranges.

U.S. Pat. Nos. 4,393,231 and 4,481,149 (Misakl et al.) describe achiralperfluoroalkyl substituted phenyl benzoate ester liquid crystalcompounds. Such achiral compounds cannot exhibit chiral smecticmesophases and cannot be used as ferroelectric liquid crystal materials.

V. V. Titov and co-workers have published a number of papers describingfluorinated liquid crystal materials. Titov et al. postulated thatreplacement of hydrogen atoms with fluorine atoms might cause a changeof intermolecular interaction and consequently mesomorphic propertiesowing to geometric and electronic factors. Two representative papers,[Molecular Crystals Liquid Crystals, Vol. 67, pp 235-240 (1981) and Vol.47, pp 1-5 (1978)], describe four partially fluorinated alkoxy andseveral perfluorinated alkyl and alkoxy substituted liquid crystalmaterials. None of these compounds are optically active and, thus,cannot possess ferroelectric properties.

U.S. Pat. No. 4,256,656 (Beguin et al.) discloses substituted phenylbenzoate esters where one of the phenyl rings is fluorinated. Thesecompounds are not chiral and therefore cannot exhibit ferroelectricbehavior. Also, ring fluorination enhances the formation of theundesired nematic mesophase.

Mahler, Walter, et al., in "Smectic Liquid Crystal from(Perfluorodecyl)decane," Mol. Cryst. Liq. Cryst. Letters, Vol. 2(3-4),1985, pp 111-119, disclose the smectogenic ability of(perfluorodecyl)decane, F(CF₂)₁₀ (CH₂)₁₀ H. This compound exhibits asmectic B liquid crystal phase, but is not chiral and therefore cannotexhibit ferroelectric behavior.

SUMMARY OF THE INVENTION

The present invention provides compounds comprising a fluorocarbonterminal portion and a chiral hydrocarbon terminal portion, the terminalportions being connected by a central core, the compounds having tiltedsmectic mesophases or having latent tilted smectic mesophases whichdevelop when said compounds having said latent mesophases are inadmixture with said compounds having tilted smectic mesophases or othersaid compounds having latent tilted smectic mesophases. These compoundshave suppressed cholesteric, i.e., chiral nematic, mesophases. Thefluorocarbon terminal portion can be represented by the formula -DC_(q)F_(2q) X where X is hydrogen or fluorine, q is 1 to 20, and D is##STR1## --O--(CH₂)_(r) --, --(CH₂)_(r) --, --OSO₂ --, --SO₂ --, --SO₂--(CH₂)_(r) --, --O(CH₂)_(r) --O(CH₂)_(r') --, ##STR2## where r and r'are independently 1 to 20 and p is 0 to 4. These compounds have greatlyenhanced smectogenic properties, lower birefringences, and longer pitchlength than their non-fluorine-containing analogues, as well as, fastswitching times. These properties make these materials useful in abroader range of devices having less restrictive design parameters thanwith previously known ferroelectric liquid crystal compounds. Further,mixtures of the compounds of the invention can be formulated to providedesired transition temperatures and broad mesophase temperature ranges.The present invention further provides precursor compounds useful in thepreparation of the ferroelectric liquid crystals.

The present invention still further provides a process for preparing theferroelectric liquid crystals of the invention. The present inventionalso relates to ferroelectric liquid crystal devices containing thechiral smectic fluorinated compounds.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to chiral compounds havingfluorine-containing terminal groups and compounds related thereto foruse as liquid crystal materials. Compounds of this invention are tiltedchiral smectic, i.e., ferroelectric, liquid crystals, liquid crystalenhancers, or liquid crystal modifiers. Tilted chiral smectic liquidcrystal molecules, such as chiral smectic C or H, are known to beferroelectric, i.e., possessing a permanent polarization perpendicularto the director or long axis of the molecule. Because these chiralsmectic materials exhibit a non-zero net polarization in the bulk, thereis a stronger coupling of this polarization with an applied electricfield than when there is only dielectric anisotropic coupling. It isthis stronger coupling in an applied electric field that provides themolecules with an ability to orient readily with greatly reducedswitching time.

Ferroelectric or tilted chiral smectic molecules orient themselves inlayers. Because of the chirality of ferroelectric materials, thedirectors spiral about an axis normal to the layers. The distancerequired for a complete 2π rotation of the director is called the pitchlength. To produce a surface-stabilized ferroelectric liquid crystaldevice as in U.S. Pat. No. 4,367,924 (Clark et al.), it is necessary tosuppress the formation of this 2π rotation, i.e., helix. This isaccomplished by using the appropriate boundary conditions and geometryas are well-known in the art.

In fabricating such a surface-stabilized ferroelectric liquid crystaldevice, the ferroelectric liquid crystal materials or mixtures thereofare placed between two bounding plates, usually glass, the insidesurfaces of which have electrodes applied and at least one of which istransparent. The electrode configuration can be a single electrode, apatterned electrode, x-y electrodes forming addressable pixels or thelike. The boundary conditions on the inside surfaces of the plates, nextto the ferroelectric liquid crystal material(s) must be prepared byshearing or rubbing an applied polymer alignment layer, or the like, asis well-known in the art, so as to orient the director of theferroelectric liquid crystal molecules parallel to the glass plates, andto orient the layers of the bulk ferroelectric liquid crystalperpendicular to the glass plates. The spacing between the plates issuch that the plates are separated by a distance of less than the pitchof the helix, resulting in suppression of helix formation. The platesare sealed around the edges and a driving electrical circuit isconnected to the plate electrodes. Two stable states of directororientation exist, each state dependent upon the direction of theapplied electric field across the conductive electrodes. In the firststable state, the polarization is aligned in one direction, while in theother stable state the director has been rotated through twice thematerial tilt angle and the polarization is in the direction opposite tothat in the first stable state. The "material tilt angle" is that anglebetween the director and the layer normal. The device is placed betweencrossed polarizers and oriented with one of the polarizers aligned withone of the stable states. Application of an electric field changes thetransmission of the device from, for example, a minimally transmittingstate to a highly transmitting state and reversal of the field willreturn the device to the minimally transmitting state. The result is afast switching ferroelectric liquid crystal device wherein the helix isunwound even in the absence of an electric field and which device can bebistable.

The compounds of this invention are also useful in non-surfacestabilized ferroelectric liquid crystal display devices. Suchnon-surface-stabilized devices are fabricated in the same manner as thesurface-stabilized devices except that the distance between the platesis greater than the helix pitch length. These non-surface-stabilizeddevices can never be bistable because the material returns to a helicalstructure in the absence of an applied electrical field.

The compounds of this invention are also useful in optically addressedliquid crystal display devices. In such devices, one of the plates isreplaced with a structure containing a photoconductive material such ascadmium sulfide and the device is optically addressed, i.e., activatedby light. Such a device, described for use with nematic liquid crystalmaterial is disclosed by Efron, U., et al., in "The Silicon LiquidCrystal Light Valve," J. Appl. Phys. 57(4), 1985, pp 1356-1368, which isincorporated herein by reference. This device is equally suitable foruse with the chiral smectic liquid crystal materials of the presentinvention.

Light transmission through a surface-stabilized device with twopolarizers is represented by the following equation:

    I=I.sub.o [sin.sup.2 (4θ)] [sin.sup.2 (πΔnd/λ)]

where

Io=transmission through parallel polarizers

θ=material tilt angle

Δn=liquid crystal birefringence

d=device spacing

λ=wavelength of light

To maximize the transmission, both sin² (4θ) and sin² (πΔnd/λ) must beat maximum. This occurs when each sin² term equals one. The first termwill be a maximum when 4θ=π/2 or when θ=22.5°. This is a function of theliquid crystal and is constant for a given material at a giventemperature. The compounds of this invention have typical θ values from17° to 40°. The second term is maximum when πΔnd/λ=π/2 or Δnd=λ/2.

This demonstrates the criticality of the low birefringence of thematerials of this invention, which low birefringence allows a largerdevice thickness, d, for a given wavelenth of light. The long pitchlength of the materials of this invention make it possible to takeadvantange of the above relationship. Thus, because of the longer pitchlength and lower birefringence of these materials, compared to presentlyavailable materials, a larger plate spacing is possible while stillmaximizing transmission, allowing easier device construction.

The fluorine-containing chiral compounds of the present invention can berepresented by the general formula: ##STR3## where M, N, and P are eachindependently ##STR4## a, b, and c are each independently zero or aninteger of from 1 to 3 with the proviso that the sum of a+b+c be atleast 2;

each A and B are independently nil, ##STR5## --CH₂ CH₂ --, --CH═CH--,--C.tbd.C--, --CH═N--, --CH₂ --O--, ##STR6## or --O--; each X, Y and Zare independently --H, --Cl, --F, --OCH₃, --CH₃, --OH, --Br, --I, --NO₂,or --CN; each l, m, and n are independently zero or an integer of 1 to4;

D is ##STR7## --O--(CH₂)_(r) --, --(CH₂)_(r) --, --OSO₂ --, --SO₂ --,--SO₂ --(CH₂)_(r))--, --O(CH₂)_(r) --O(CH₂)_(r') --, ##STR8## where rand r' are independently 10 to 20, and p is 0 to 4;

R is --OC_(q) H_(2q) --OC_(q') H_(2q'+1') --C_(q) H_(2q) --O--C_(q')H_(2q'+1') --C_(q) H_(2q) --R', --O--C_(q) H_(2q) --R', ##STR9## whereR' is --Cl, --F, --CF₃, --NO₂, --CN, --H, ##STR10## and q and q' areindependently 1 to 20 with the proviso that R is chiral; and

R_(f) is --C_(q) F_(2q) --X or --C_(q) F_(2q) --O--C_(q') F_(2q') --Xwhere X is H or F, and q and q' are independently 1 to 20.

Several of the compounds of the above formula were observed to not havesmectic phases as single components upon cooling from the isotropicphase. Upon further investigation it was found that these compounds,when mixed with other liquid crystals or other compounds of the aboveformula, did show a desired tilted smectic phase and, thus, exhibit aphenomenon termed herein "latent tilted smectic mesophases". It issuspected that these compounds may have monotropic smectic phases attemperatures below their crystallization points. By the Phase Rule formixtures, these smectic phases will appear at different mixture ratios,which ratios can be readily determined by those skilled in the art.

Chiral smectic liquid crystal compounds of this invention have a numberof desirable properties. Chain fluorination induces a higher order inthe molecule than the non-fluorine containing analogs and thuscholesteric mesophases are lost and smectic mesophases are introduced orenhanced. It is believed that the incompatibility of the fluorophilicportions, i.e., the fluorine-containing terminal portions, and thefluorophobic portions, i.e., the hydrocarbon core and terminal portions,of the materials lead to the higher ordering. This belief is buttressedby the fact that introduction of a hydrogen atom on the terminal carbonatom of a perfluorinated chain generally results in a narrower smecticphase range and a lowering of the clearing point due to unfavorabledipole-dipole interactions at the smectic layer interface.

The compounds of this invention have longer pitch lengths and lowerbirefringences than the non-fluorinated analogs and, thus, are veryuseful in the fabrication of ferroelectric liquid crystal devices. Insuch devices, at thicknesses less than about 50 microns, unusual chiralsmectic textures are observed by optical microscopy, the texturesgenerally being devoid of pitch lines.

It is suspected that the packing of the liquid crystal materials of theinvention is in an interdigitated structure. Cross-sectional molecularareas of fluorocarbon chains are about 11/2 to 2 times those ofhydrocarbon chains. Thus, the structure of each layer can have closepacking with interdigitation of the hydrocarbon core and terminal chainsand the outer portion of each layer formed by the fluorocarbon chains.This hypothesis is further suggested by small angle X-ray scatteringmeasurements which indicate that layer spacing is only somewhat greater,i.e., about 20 to 60 percent greater than the extended length of themolecule for a given material at a given temperature.

The materials of this invention have good chemical stability towardswater, weak acids and weak bases. They do not undergo degradation duringnormal use in a device. They are photo-chemically stable in that they donot easily undergo photochemical reactions. They are generally colorlesscompounds with no absorption in the visible spectrum.

When these compounds are used in mixtures, a lowering of transitiontemperatures is observed accompanied by an insignificant clearing pointtemperature change which leads to a broader temperature range for themesophases observed.

For the phenyl benzoate ester series of compounds, thesmectic-mesophases are observed for shorter alkyl and alkoxy terminalchain lengths than for the non-fluorinated analogs.

The novel precursor compounds, useful in the preparation of theferroelectric liquid crystals of the invention, are those which can berepresented by the formula: ##STR11## where Q is --Cl or --OCH₃, x is 4to 20 and the compounds are chiral, and compounds represented by theformula ##STR12## where J is --OH, --COOH, or --CHO, y is 1 to 20, z andz' are independently 1 to 20, and R"' is an alkyl group having 1 to 4carbon atoms.

The compounds of the invention can be readily prepared by (1) mixing atleast one compound represented by the formula ##STR13## with at leastone compound represented by the formula ##STR14## or (2) mixing at leastone compound represented by the formula ##STR15## with at least onecompound represented by the formula ##STR16## where P, M, N, and P areeach independently ##STR17##

a, b, and c are each independently zero or an integer of from 1to 3 withthe proviso that the sum of a+b+c be at least 2;

each A and B are independently nil, ##STR18## --CH═N--, --CH₂ --O--,##STR19## --O--, --CH₂ --CH₂ --, --CH═CH--, or --C.tbd.C--;

each A', A", B' and B" are independently --OH, --COOH, --SH, --SeH,--TeH, --NH₂, --COCl, --CHO, or --CH₂ COOH, with the proviso that A' canenter into an addition or condensation reaction with A" and B' can enterinto an addition or condensation reaction with B";

each X, Y and Z are independently --H, --Cl, --F, --OCH₃, --OH, --Br,--I, --CH₃, --NO₂ or --CN;

each l, m and n are independently zero or an integer of 1 to 4;

R is --OC_(q) H_(2q) --OC_(q') H_(2q'+1') --C_(q) H_(2q) --O--C_(q')H_(2q'+1') --C_(q) H_(2q) --R', --O--C_(q) H_(2q) --R', ##STR20## whereR' is --H, --Cl, --F, --CF₃, --NO₂, --CN ##STR21## and q and q' areindependently 1 to 20, with the proviso that R is chiral;

D is ##STR22## --O--(CH₂)_(r) --, --(CH₂)_(r) --, --OSO₂ --, --SO₂ --,--SO₂ --(CH₂)_(r) --, --O(CH₂) _(r) --O(CH₂)_(r') --, ##STR23## where rand r' are independently 1 to 20, and p is 0 to 4;

R_(f) is --C_(q) F_(2q) --X or --C_(q) F_(2q) --O--C_(q') F_(2q') --X,where X is

H or F, and q and q' are independently 1 to 20; and allowing said A' andA" or B' or B" to react in the presence of suitable coupling agents asis well-known to those skilled in the art. For example, if A', or B', is--COOH and A", or B", is --OH, the compounds are coupled in a suitablesolvent system using N,N'-dicyclohexylcarbodiimide and4-(N,N-dimethylamino)pyridine catalyst; if A', or B', is --COCl and A",or B", is --OH, --SH, --SeH, or --TeH, the compounds are coupled in asuitable solvent using triethylamine base; if A', or B', is --CHO andA", or B" is --NH₂, the compounds are coupled in anhydrous solvent usingan acid catalyst under reflux.

The compounds of this invention are either liquid crystals themselvesand can be used as such or in mixtures with other liquid crystals; or ifnot liquid crystalline above their crystallization temperatures, areuseful in admixture with other liquid crystals to modify or enhancetheir properties. The compounds of the invention are also useful when inadmixture with pleochroic dyes in a guest-host mixture. These mixturesprovide color to the liquid crystal devices, enhance the contrast andbrightness, and eliminate the need for one device polarizer as is wellknown in the art.

EXAMPLES

In the following examples, the trifluoromethylsulfonate esters wereprepared using the method of U.S. Pat. No. 3,419,595 except thattrifluoromethanesulfonic anhydride was used in place oftrifluoromethanesulfonyl fluoride; the S-2-methylbutyl, S-4-methylhexyl,and R-1-methylheptyl tosylates were prepared following the reactionscheme in Mol. Cryst. Liqa. Cryst., 1984, 114, 237-247; the4-benzyloxy-4'-hydroxybiphenyl was prepared as described in U.S. Pat.No. 4,614,609, Example 25(i) except that benzyl chloride was substitutedfor the (+)-2-methylbutyl bromide; the 2-chloro-4-methylpentanoic acidwas prepared as described in J. Org. Chem., 51, 1986, 242-245; theS-2-methylbutyl-4-hydroxybenzoate was prepare as described in LiquidCrystals and Ordered Fluids, ed. Griffin, A. C. et al., 4, 1984, p.1-42; the S-4-(2-methylbutyl)phenol was prepared as described in U.S.Pat. No. 4,195,916; all acid chlorides were prepared by reacting theappropriate carboxylic acid with an excess of thionyl chloride underreflux, followed by removal of the excess thionyl chloride anddistillation or recrystallization of the acid chloride; and all alkylbromides were prepared by treating the corresponding alcohol withbromine in the presence of triphenylphosphine, as disclosed in J. Am.Chem. Soc., 86, 1964, p. 964-965.

Examples 1-68 describe procedures for preparing intermediate compoundsuseful in preparing the liquid crystal compounds of this invention.Examples 69-139 describe preparation of the liquid crystal compounds ofthis invention. Examples 140-169 describe mixture formulations withmaterials possessing a latent chiral smectic mesophase. Examples 170-175describe multicomponent mixture formulations utilizing liquid crystalcompounds of this invention in liquid crystal devices.

EXAMPLE 1

Sodium methylate was prepared by reacting sodium (2.3 g, 0.1 mol) with100 ml anhydrous methanol. To the sodium methylate was added methyl4-hydroxybenzoate (15.2 g, 0.1 mol). Excess methanol was removed underreduced pressure and toluene was added and removed under reducedpressure to remove any residual methanol. The solid residue wasdissolved in 2:1 toluene-dimethylformamide and S-4-methylhexyl bromide(17.9 g, 0.1 mol) was added as a single portion and the mixture wasrefluxed for 1 day. The reaction product was cooled and washed 3 timeswith 100 ml water. The organic layer was dried over anhydrous MgSO₄,filtered, and concentrated. This crude methylS-4-(4-methylhexyloxy)benzoate was refluxed in 100 ml of 10% aqueoussodium hydroxide for 1 day. The reaction product was cooled to roomtemperature (25° C.) and acidified with concentrated aqueous HCl. Theprecipated solid was collected by filtration and washed several timeswith cool water. This material was purified by recrystallization fromethanol-water. S- 4-(4-Methylhexyloxy)benzoic acid (20 g, 85% yield) wasobtained. NMR and MS were consistent for the product.

EXAMPLES 2-6

In Examples 2-6, compounds were prepared as in Example 1 except that inExample 2 (15.2 g, 0.1 mol) methyl 4-hydroxybenzoate was used andS-2-methylbutyl bromide (15.1 g, 0.1 mol) was substituted for theS-4-methylhexyl bromide, in Example 3, methyl 3-chloro-4-hydroxybenzoate(5.6 g, 30 mmol) was substituted for the methyl 4-hydroxybenzoate andS-4-methylhexyl tosylate (8.1 g, 30 mmol) was substituted for theS-4-methylhexylbromide, in Example 4 methyl 3-methoxy-4-hydroxybenzoate(6.07 g, 33 mmol) was substituted for the methyl 4-hydroxybenzoate andS-4-methylhexyltosylate (9.0 g, 33 mmol) was substituted for theS-4-methylhexyl bromide in Example 5, (30.4 g, 0.1 mol)methyl-4-hydroxybenzoate was used and benzyl chloride (27.5 g, 0.22 mol)was substituted for the S-4-methylhexyl bromide, in Example 6, (3.04 g,0.02 mol methyl-4-hydroxybenzoate was used and R-1-methylheptyl tosylate(5.68 g, 0.02 mol) was substituted for the S-4-methylhexyl bromide. Thecompounds thus-produced were S-4-(2-methylbutyloxy)benzoic acid (Example2), S-3-chloro-4-(4-methylhexyloxy)benzoic acid (Example 3),S-3-methoxy-4-(4-methylhexyloxy)benzoic acid (Example 4),4-benzyloxybenzoic acid (Example 5), andS-4-(1,'-methylheptyloxy)benzoic acid (Example 6).

EXAMPLE 7

Sodium hydride (1.2 g, 50 mmol) was suspended in 10 mL anhydroustetrahydrofuran and S-2-methylbutanol (4.4 g, 50 mmol) was addeddropwise. Upon completion of the addition, the reaction was stirred for1 hour at room temperature. The solution was cooled to -78° C. andα-bromotolunitrile (9.8 g, 50 mmol) was added dropwise. The reaction wasallowed to warm to room temperature and then refluxed for 1 day. Thetetrahydrofuran was removed under reduced pressure and toluene added tothe residue. This solution was washed 3 times with water, dried overanhydrous magnesium sulfate, filtered, and concentrated. TheS-α-(2-methylbutyl)tolunitrile was vacuum distilled. This material wasdissolved in 40 ml of methanol and 100 ml water containing 4 g NAOH and4 g KOH was added. The resulting mixture was refluxed for 2 days andthen acidified with 12N HCl. The precipitated S-α-(2-methylbutyl)toluicacid was collected by filtration and recrystallized from ethanol to give9.8 g of product.

EXAMPLE 8

Sodium methylate was prepared by reacting sodium (0.58 g, 25 mol) with25 ml anhydrous methanol. To the sodium methylate was added methyl4-hydroxybenzoate (3.8 g, 25 mol). Excess methanol was removed underreduced pressure and toluene was added and removed under reducedpressure to remove any residual methanol. The solid residue wasdissolved in 2:1 toluene-dimethyl formamide and1,1-dihydroperfluorobutyl trifluoromethylsulfonate (8.3 g, 25 mmol) wasadded as a single portion and the mixture was refluxed for 1 day. Thereaction product was cooled and washed 3 times with 100 ml water. Theorganic layer was dried over anhydrous MgSO₄, filtered, andconcentrated. This crude methyl 4-(1,1-dihydroperfluorobutyloxy)benzoatewas refluxed in 100 ml of 10% aqueous sodium hydroxide for 1 day. Thereaction product was cooled and acidified with concentrated aqueous HCl.The precipated solid was collected by filtration and washed severaltimes with cool water. This material was purified by recrystallizationfrom ethanol-water. 4-(1,1-dihydroperfluorobutyloxy)benzoic acid (6.42g, 80% yield) having a melting range of 182° to 1830° C. was obtained.

EXAMPLES 9-15

In Example 9, compounds were prepared as in Example 6 except that inExample 8 (3.8 g, 25 mmol) methyl 4-hydroxybenzoate was used and1,1-dihydroperfluorohexyl trifluoromethylsulfonate (10.8 g, 25 mmol) wassubstituted for the 1,1-dihydroperfluorobutyl trifluoromethyl sulfonate,in Example 10 (3.8 g, 25 mmol) methyl 4-hydroxybenzoate was used and1,1-dihydroperfluorooctyl trifluoromethylsulfonate (13.3 g, 25 mmol) wassubstituted for the 1,1-dihydroperfluorobutyl trifluoromethylsulfonate,in Example 11 (3.04 g, 20 mmol) methyl 4-hydroxybenzoate was used and1,1,7-trihydroperfluoroheptyl trifluoromethylsulfonate (9.28 g, 20 mmol)was substituted for the 1,1-dihydroperfluorobutyltrifluoromethylsulfonate, in Example 12 methyl3-chloro-4-hydroxybenzoate (2.79 g, 15 mmol) was substituted for themethyl 4-hydroxybenzoate and 1,1-dihydroperfluorohexyltrifluoromethylsulfonate (6.48 g, 15 mmol) was substituted for the1,1-dihydroperfluorobutyl trifluoromethylsulfonate, in Example 131,1-dihydroperfluorohexyl trifluoromethylsulfonate (12.6 g, 30 mmol) wassubstituted for the 1,1-dihydroperfluorobutyl trifluoromethylsulfonate,and methyl 3-methoxy-4-hydroxybenzoate (5.46 g, 30 mmol was substitutedfor the methyl 4-hydroxybenzoate in Example 14, methyl2-chloro-4-hydroxybenzoate (7.00 g, 0.0375 mol) was substituted for themethyl 4-hydroxybenzoate and 1,1-dihydroperfluorobutyltrifluoromethylsulfonate (13.28 g, 0.040 mol) was used, and in Example15, methyl 2-chloro-4-hydroxybenzoate (1.87 g, 0.01 mol) was substitutedfor the methyl 4-hydroxybenzoate and 1,1-dihydroperfluorooctyltrifluoromethylsulfonate (5.32 g, 0.01 mol) was substituted for the1,1-dihydroperfluorobutyl trifluoromethylsulfonate. The compoundsthus-produced were 4-(1,1-dihydroperfluorohexyloxy)benzoic acid (Example9), 4-(1,1-dihydroperfluorooctyloxy)benzoic acid (Example 10),4-(1,1,7-7-trihydroperfluoroheptyloxy)benzoic acid (Example 11),3-chloro-4-(1,1-dihydroperfluorohexyloxy)benzoic acid (Example 12), and3-methoxy-4-(1,1-dihydroperfluorohexyloxy)benzoic acid (Example 13),2-chloro-4-(1,1-hydroxyperfluorobutoxy)benzoic acid (Example 14), and2-chloro-4 -(1,1-dihydroperfluorooctyloxy)benzoic acid (Example 15).

EXAMPLE 16

Sodium methylate was prepared by reacting sodium (2.3 g, 0.1 mol) with100 ml of anhydrous methanol. To the sodium methylate was addedmonotetrahydropyranylether of hydroquinone (19.4 g, 0.1 mol). Excessmethanol was removed under reduced pressure and the residue wasdissolved in 100 ml of 2:1 toluene-dimethylformamide. S-4-methylhexylbromide (17.9 g, 0.1 mol) was added and the mixture was refluxed for 1day. The reaction product was cooled and washed 4 times with 100 mlwater and concentrated. The residue was treated with 100 ml 0.5M HCl for18 hours. Ether was added and the ethereal solution was washed 3 timeswith water, dried over anhydrous MgSO₄, filtered and concentrated. Thecrude product was distilled and S-4-(4-methylhexyloxy)phenol (11.8 g,boiling range 142°-145° C./0.8 mm) was obtained.

EXAMPLE 17

In Example 17 a compound was prepared as in Example 16 except that inExample 17 (48.5 g, 0.25 mol) monotetrahydropyranylether of hydroquinonewas used and S-2-methylbutyl bromide (38 g, 0.25 mol) was substitutedfor the S-4-methylhexyl bromide. The thus-produced product wasS-4-(2-methylbutyloxy)phenol.

EXAMPLE 18

Sodium hydride (0.12 g, 5 mmol) was suspended in 20 mldimethylformamide. Monobenzylhydroquinone (1.0 g, 5 mmol) in 20 mltoluene was added. When the evolution of hydrogen ceased,1-bromo-11-perfluorooctylundecane (2.37 g, 5 mmol) was added. Themixture was stirred and refluxed for 1 day. The reaction was cooled toroom temperature and poured into 100 ml water, and extracted with ether.The ethereal extract was washed once with 1N sodium hydroxide, once withwater, dried over anhydrous MgSO₄, filtered, and concentrated. Thiscrude intermediate was dissolved in 150 ml 2:1 anhydrous ethanol-ethylacetate and hydrogenated using 0.6 g 10% palladium on carbon and ahydrogen pressure of 500 kPa at room temperature for 4 hours. Thecatalyst was removed by filtration and the solvents were removed underreduced pressure. The product,1-(4-hydroxyphenoxy)-11-perfluorooctylundecane, weighed 2.6 g (76%yield).

EXAMPLES 19-20

In Examples 19-20 the compounds were prepared as in Example 18 exceptthat in Example 19, (2.0 g, 10 mmol) of monobenzylhydroquinone was used,and N-ethyl-N-(2-tosylethyl)perfluorooctylsulfonamide (7.31 g, 10 mmol)was substituted for 1-bromo-11-perfluorooctylundecane, and in Example20, (10.0 g, 0.05 mol) monobenzylhydroquinone was used andR-1-methylheptyl tosylate (14.2 g, 0.05 mol was substituted for the1-bromo-11-perfluorooctylundecane. The compounds thus-produced wereN-ethyl-N-[(2-(4-hydroxyphenoxy)ethyl] perfluorooctylsulfonamide(Example 19) and S-4-(1-methylheptyloxy)phenol (Example 20).

EXAMPLE 21

Sodium hydride (5.0 g, 0.21 mol) was suspended in 150 ml dry glyme.Monobenzylhydroquinone (40 g, 0.20 mol) was dissolved in 500 mlanhydrous glyme and added dropwise to the sodium hydride with stirringunder nitrogen atmosphere. Upon completion of the addition, the mixturewas stirred at room temperature for 1 hour and then cooled to -78° C.1,1-Dihydroperfluorobutyl trifluoromethylsulfonate (70.0 g, 0.21 mol)was then added dropwise and, upon completion of the addition, thereaction was allowed to warm slowly to room temperature. The glyme wasremoved under reduced pressure and 800 ml of water and 700 ml of ethylether were added to the residue and mixed vigorously. The ether layerwas separated and washed twice with 5% sodium hydroxide, and twice withwater, dried over anhydrous MgSO₄, filtered and concentrated. A lightorange-brown product (65 g) was obtained. This crude intermediate wasdissolved in anhydrous ethanol and hydrogenated using 10% palladium oncarbon and a hydrogen pressure of 500 kPa at room temperature for 2hours. The catalyst was removed by filtration and the ethanol wasremoved under reduced pressure. The crude phenolic product was purifiedby high performance liquid chromatography (HPLC) using a prepacked 500ml volume silica gel column and methylene chloride as eluent andrecrystallization from petroleum ether.4-(1,1-dihydroperfluorobutyloxy)phenol (34.63 g, 59.3% yield) wasobtained.

EXAMPLES 22-28

In Examples 22-28, compounds were prepared as in Example 21 except thatin Example 22 (20.0 g, 0.1 mol) monobenzylhydroquinone was used and1,1-dihydroperfluorohexyl trifluoromethylsulfonate (45.0 g, 0.105 mol)was substituted for the 1,1-dihydroperfluorobutyltrifluoromethylsulfonate, in Example 23, (20.0 g, 100 mmol)monobenzylhydroquinone was used and 1,1-dihydroperfluorooctyltrifluoromethylsulfonate (58.5 g, 110 mmol) was substituted for the1,1-dihydroperfluorobutyl trifluoromethylsulfonate, in Example 24 (10 g,50 mmol) monobenzylhydroquinone was used and1,1,2,2-tetrahydroperfluorohexyl trifluoromethylsulfonate (19.8 g, 50mmol) was substituted for the 1,1-dihydroperfluorobutyl trifluoromethylsulfonate, in Example 25 (3.5 g, 17.5 mmol) monobenzylhydroquinone wasused and 1,1,7-trihydroperfluoroheptyl trifluoromethylsulfonate (8.1 g,17.5 mmol) was substituted for the 1,1-dihydroperfluorobutyltrifluoromethylsulfonate, in Example 26 (4.0 g, 20 mmol)monobenzylhydroquinone was used and 1,1,11-trihydroperfluoroundecyltrifluoromethylsulfonate (3.66 g, 18.3 mmol) was substituted for the1,1-dihydroperfluorobutyl trifluoromethylsulfonate, in Example 27 (3.66g, 18.3 mmol) monobenzylhydroquinone was used and2-(1,1-dihydroperfluorooctyloxy)ethyl trifluoromethylsulfonate (10.5 g,18.3 mmol) was substituted for the 1,1-dihydroperfluorobutyltrifluoromethylsulfonate, and in Example 28 (20.0 g, 0.1 mol)monobenzylhydroquinone was used and 1,1-dihydroperfluoroethyltrifluoromethylsulfonate (23.2 g, 0.1 mol) was substituted for the1,1-dihydroperfluorobutyl trifluoromethylsulfonate. The thus-producedproducts were 4-(1,1-dihydroperfluorohexyloxy)phenol (Example 22),4-(1,1-dihydroperfluorooctyloxy)phenol (Example 23),4-(1,1,2,2-tetrahydroperfluorohexyloxy)phenol (Example 24),4-(1,1,7-trihydroperfluoroheptyloxy)phenol (Example 25),4-(1,1,11-trihydroperfluoroundecyloxy)phenol (Example 26),1-(4-hydroxyphenoxy-2-(1,1,-dihydroperfluorooctyloxy)ethane (Example27), and 4-(1,1-dihydroperfluoroethoxy)phenol (Example 28).

EXAMPLE 29

4-Bromophenol (8.65 g, 0.05 mol) was dissolved in 25 ml dry glyme andadded dropwise to a suspension of sodium hydride (1.2 g, 0.05 mol) in 25ml anhydrous glyme. Upon completion of the addition, the mixture wasstirred at room temperature for 30 minutes and 25 ml of dry dimethylformamide was added. S-4-methylhexyl bromide (8.95 g, 0.05 mol) was thenadded and the mixture refluxed for 1 day. The reaction was filtered andthe glyme removed under reduced pressure. Methylene chloride (50 ml) wasadded to the residue and this solution was washed once with water, oncewith 5% sodium hydroxide, and again with water, dried over anhydrousMgSO₄ filtered, and concentrated under reduced pressure. Distillationgave 12.1 g of S-1-bromo-4-(4-methylhexyloxy)benzene having a boilingrange of 158°-163° C./9 mm.

EXAMPLE 30

In Example 30, the procedure of Example 29 was followed except that(17.3 g, 0.1 mol) of 4-bromophenol was used and S-2-methyl butyl bromide(15.1 g, 0.1 mol) was substituted for the S-4-methylhexyl bromide toproduce S-1-bromo-4-(2-methylbutyloxy)benzene.

EXAMPLE 31

Magnesium (2.66 g, 0.111 mol) was placed in a 250 ml flask and stirredwithout solvent for 15 minutes under dry nitrogen. Anhydroustetrahydrofuran (THF) (100 ml) was then added to the flask.S-1-bromo-4-(4-methylhexyloxy)benzene (30.0 g, 0.111 mol) in 50 ml THFwas placed in an addition funnel and 25% of this solution was run intothe flask. This mixture was warmed carefully and when the reaction hadbegun, the heat was removed and the rate of reflux was controlled by therate of addition of the remainder of theS-1-bromo-4-(4-methylhexyloxy)benzene solution. Upon completion of theaddition, the reaction was refluxed for 2 hours, cooled to just belowreflux and sulfur (3.4 g, 0.106 mol) was added very carefully inportions. Upon completion of the addition of the sulfur, the reactionwas stirred at room temperature for 3 hours, filtered, and concentrated.Ethyl ether (200 ml) was added and 1M HCl was carefully added withvigorous stirring. The ether layer was separated and washed again with1M HCl washed once with water, dried over anhydrous MGSO₄, filtered, andconcentrated. The crude product was distilled, yieldingS-4-(4-methylhexyloxy)thiophenol (15.1 g, 63% yield) having a boilingrange of 142°-50° C./3mm.

EXAMPLES 32-33

In Examples 32-33, the procedure of Example 31 was followed except thatin Example 32 S-1-bromo-4-(2-methylbutyloxy)benzene (21.7 g, 0.089 mol)was substituted for the S-1-bromo-4-(4-methylhexyloxy)benzene to produceS-4-(2-methylbutyloxy)thiophenol and in Example 33,S-1-bromo-4-(2-methylbutoxy)benzene (2.67 g, 0.011 mol) was substitutedfor the S-1-bromo-4-(4-methylhexyloxy)benzene, and selenium (0.79 g,0.010 mol) was substituted for the sulfur to produceS-4-(2-methylbutoxy)selenophenol.

EXAMPLE 34

Under a nitrogen atmosphere, chlorosulfonic acid (120 g, 1.03 mol) wascooled to -5° C. (+)-2-methylbutyl benzene (30 g, 0.20 mol) was addeddropwise at a rate such that the temperature did not rise above 0° C.Upon completion of the addition, the reaction was stirred for 4 hours at0° C. The solution was then carefully poured over 300 g of crushed ice.The resulting oil was washed with H₂ O and then dissolved in a mixtureof 130 ml concentrated sulfuric acid and 250 ml H₂ O and cooled to -10°C. With vigorous stirring, 40 g of zinc was added in portions such thatthe temperature of the mixture did not rise above -5° C. The mixture wasstirred at -5° C. for 30 minutes and allowed to warm to roomtemperature. The mixture was then warmed to 100° C. at which time anexotherm occurred. The mixture was maintained at 115° C. for 2 hours andthen cooled to room temperature. The mixture was filtered to removeundissolved zinc and the filtrate was extracted 3 times with ether. Thecombined organics were dried over MgSO₄. The dessicant was removed byfiltration and the ether removed on a rotary evaporator. The residue wasdistilled under reduced pressure and the S-4-(2-methylbutyl)thiophenolcollected at 93°-95° C. at 1.2 mm Hg.

EXAMPLE 35

Sodium methylate was prepared by reacting sodium (1.15 g, 50 mol) with50 ml anhydrous methanol. To the sodium methylate was added4-hydroxybenzaldehyde (6.1 g, 50 mmol). Excess methanol was removedunder reduced pressure. The solid residue was dissolved in 2:1toluene-dimethyl formamide and 1,1-dihydroperfluorohexyltrifluoromethylsulfonate (21.6 g, 50 mmol) was added all at once and themixture refluxed for 1 day. The reaction was cooled and washed 3 timeswith 100 ml water. The organic layer was dried over anhydrous MGSO₄,filtered and concentrated. Distillation of this material produced4-(1,1-dihydroperfluorohexyloxy)benzaldehyde (13.1 g, 65% yield) havinga boiling range of 91°-92° C./0.2mm.

EXAMPLES 36-37

In Examples 36 and 37, compounds were prepared as in Example 35 exceptthat in Example 36 1,1-dihydroperfluorobutyl trifluoromethylsulfonate(33.2 g, 100 mmol) was substituted for the 1,1-dihydroperfluorohexyltrifluoromethylsulfonate to produce4-(1,1-dihydroperfluorobutyloxy)benzaldehyde and in Example 371,1-dihydroperfluorooctyl trifluoromethylsulfonate (13.3 g, 5 mmol) wassubstituted for the 1,1-dihydroperfluorohexyl trifluoromethylsulfonateto produce 4-(1,1-dihydroperfluorooctyloxy)benzaldehyde.

EXAMPLE 38

Sodium hydride (40 mmol) was suspended in anhydrous dimethyl formamideand 2,6-dihydroxynapthalene (20 mmol) was added. Upon completion of theevolution of hydrogen, S-4-methylhexyl tosylate (10 mmol) was added andthe mixture refluxed for 1 day. The reaction product was acidified withaqueous HCl and extracted with ether. The ether extract was washed withwater to remove the dimethyl formamide, dried over anhydrous MgSO₄,filtered, and concentrated. The crude product was purified by flashchromatography in 80:20 hexane:ethyl acetate on silica gel to yieldS-6-(4-methylhexyloxy)-2-naphthol.

EXAMPLES 39 AND 40

In Examples 39 and 40, compounds were prepared as in Example 38 exceptthat in Example 39 1,4-dihydroxynaphthalene (20 mmol) was substitutedfor the 2,6-dihydroxynaphthalene to produceS-4-(4-methylhexyloxy)-1-naphthol and in Example 401,5-dihydroxynaphthalene (20 mmol) was substituted for the2,6-dihydroxynaphthalene to produce S-5-(4-methylhexyloxy)-1-naphthol.

EXAMPLE 41

To a suspension of sodium hydride (12 g, 0.3 mol 60% in mineral oil) in600 ml toluene and 400 ml dimethyl formamide was added2,6-dihydroxynaphthalene (80 g, 0.5 mol) and the mixture was heated toreflux over a thirty minute period. Benzyl chloride (65 ml, 71.5 g, 0.56mol) was added dropwise and the mixture was refluxed for 10 hours. Aftercooling to room temperature, the mixture was washed 6 times with waterto remove the dimethyl formamide. The resulting toluene solution waswashed twice with 150 ml 0.5N sodium hydroxide to remove unreactedstarting material and then with water and dried over anhydrous magnesiumsulfate. The magnesium sulfate was removed by filtration and thefiltrate was concentrated to 150 ml. The solid which had crystallizedwas collected by vacuum filtration and washed with a small amount oftoluene to yield 2-benzyloxy-6-hydroxynaphthalene.

EXAMPLE 42

Sodium hydride (50 mmol) was suspended in 25 ml anhydrous diglyme and2,6-dihydroxynapthalene (25 mmol) in 75 ml anhydrous diglyme was added.The mixture was warmed for 1 hour at 150° C., then cooled, and1,1-dihydroperfluorobutyl trifluoromethylsulfonate (12.5 mmol) wasadded. The mixture was warmed for 2 days at 150° C., then cooled to roomtemperature. The reaction was acidified with 3M HCl and extracted twicewith ether. The combined organic extractions were washed 4 times withwater, dried over anhydrous MgSO₄, filtered, and concentrated. The crudematerial was purified by HPLC using methylene chloride on a silica gelcolumn to give 6-(1,1-dihydroperfluorobutyloxy)-2-napthol (1.9 g, 44%yield).

EXAMPLES 43-47

In Examples 43-47, compounds were prepared as in Example 42 except thatin Example 43 1,4-dihydroxynaphthalene (3.2 g, 20 mmol) was substitutedfor the 2,6-dihydroxynaphthalene to produce4-(1,1-dihydroperfluorobutyloxy)-1-naphthol, in Example 441,4-dihydroxynaphthalene (3.2 g, 20 mmol) was substituted for the2,6-dihydroxynaphthalene and 1,1-dihydroperfluorohexyltrifluoromethylsulfonate (4.3 g, 10 mmol) was substituted for the1,1-dihydroperfluorobutyl trifluoromethylsulfonate to produce4-(1,1-dihydroperfluorohexyloxy)-1-naphthol, in Example 452,7-dihydroxynaphthalene (3.2 g, 20 mmol) was substituted for the2,6-dihydroxynaphthalene to produce7-(1,1-dihydroperfluorobutyloxy)-2-naphthol, in Example 46,4,4'-biphenol was substituted for the 2,6-dihydroxynaphthalene and1,1-dihydroperfluorooctyl trifluoromethylsulfonate was substituted forthe 1,1-dihydroperfluorobutyltrifluoromethyl sulfonate to produce4-(1,1-dihydroperfluorooctyloxy)-4'-hydroxybiphenyl, and in Example 47,4,4'-biphenol was substituted for the 2,6-dihydroxynaphthalene toproduce 4-(1,1-dihydroperfluorobutoxy)-4'-hydroxybiphenyl.

EXAMPLE 48

Sodium hydride (4.8 g, 0.2 mol) was suspended in 200 ml anhydrous glymeand S-4-methylhexanol (11.6 g, 0.1 mol) was added dropwise with stirringunder nitrogen atmosphere at room temperature. Upon completion of theaddition, 6-chloro-3-pyridine carboxylic acid (15.8 g, 0.1 mol) wasadded and this mixture was refluxed for 1 day. The reaction wasacidified with 300 ml 0.5M HCl and then extracted 3 times with ethylether. The combined ethereal extracts were then dried over anhydrousMGSO₄, filtered, and concentrated. The crude material was recrystallizedfrom heptane twice to produceS-6-(4-methylhexyloxy)-3-pyridinecarboxylic acid (17.2 g, 73% yield)containing 8 weight percent of starting 6-chloro-3-pyridinecarboxylicacid by gas chromatography.

EXAMPLES 49-51

In Examples 49-51, compounds were prepared as in Example 48 except thatin Example 49, S-2-methylbutanol (8.8 g, 0.10 mol) was substituted forthe S-4-methylhexanol to produceS-6-(2-methylbutyloxy)-3-pyridinecarboxylic acid, in Example 50,S-1-methylheptanol (13.0 g, 0.1 mol) was substituted for theS-4-methylhexanol to produceS-6-(1-methylheptyloxy)-3-pyridinecarboxylic acid and in Example 51,1,1-dihydroperfluorobutanol (6.0 g, 0.03mol) was substituted for theS-4-methylhexanol to produce6-(1,1-dihydroperfluorobutyloxy)-3-pyridinecarboxylic acid.

EXAMPLES 52 AND 53

In Example 52, S-4-(2-methylbutyl)-4'-cyanobiphenyl (10 g), washydrolyzed in methanol-water containing 8 g potassium hydroxide and 8 gsodium hydroxide for 7 days at reflux. The reaction was acidified withconcentrated HCl and the product collected by filtration and dried undervacuum to produce S-4-(2-methylbutyl)-4'-biphenyl carboxylic acid. inExample 53, the procedure of Example 52 was followed except thatS-4-(2-methylbutyloxy)-4'-cyanobiphenyl was substituted for theS-4-(2-methylbutyl)-4'-cyanobiphenyl to produceS-4-(2-methylbutyloxy)-4'-biphenyl carboxylic acid.

EXAMPLE 54

S-4-(4-methylhexyloxy)phenol (4.16 g, 0.02 mol) in 20 ml benzene wasadded dropwise at 25° C. under nitrogen atmosphere to a stirredsuspension of sodium hydride (0.80 g, 0.02 mol, 60% in mineral oil) in10 ml benzene. After completion of the addition, the mixture wasrefluxed for 1 hour and cooled to 250° C. 3,6-dichloropyridizine (2.98g, 0.02 mol) in 20 ml benzene was added dropwise under nitrogenatmosphere at 25° C. with stirring. The resulting mixture was thenrefluxed for 12 hours. The reaction was cooled and toluene (50 ml) wasadded. The reaction mixture was then washed with water 3 times, driedover anhydrous magnesium sulfate, filtered and concentrated to give 5.50g of S-3-chloro-6-[4'-(4"-methylhexyloxy)phenoxylpyridizine.

EXAMPLE 55

4-Benzyloxyphenol (10.0 g, 0.05 mol),4-(1,1-dihydroperfluorobutoxy)benzoic acid (16.0 g, 0.05 mol) preparedas in Example 8, and 4-dimethylaminopyridine (0.1 g) were dissolved in100 ml methylene chloride. Dicyclohexylcarbodiimide (11.0 g, 0.053 mol)was then added in one portion. The reaction mixture was stirred at 25°C. under nitrogen atmosphere for 12 hours. The reaction product wasfiltered, washed sequentially with 0.5N hydrochloric acid, 5% aqueoussodium bicarbonate, and water, dried over anhydrous magnesium sulfate,filtered, and concentrated to yield 22 g 4-benzyloxyphenyl4'-(1,1-dihydroperfluorobutoxy)benzoate.

EXAMPLES 56-59

In Examples 56-59, the procedure of Example 55 was followed except thatin Example 56 (1.6 g, 5 mmol) 4-(1,1-dihydroperfluorobutoxy)benzoic acidas used and 2-benzyloxy-6-naphthol (1.25 g, 5 mmol) was substituted forthe 4-benzyloxyphenol, in Example 57, (2.0 g, 10 mmol) 4-benzyloxyphenolwas used and S-4-methylhexanoic acid (1.30 g, 10 mmol) was substitutedfor the 4-(1,1-dihydroperfluorobutoxy)benzoic acid, in Example 58,4-benzyloxybenzoic acid (2.28 g, 10 mmol) was substituted for the4-(1,1-dihydroperfluorobutoxy)benzoic acid and6-(1,1-dihydroperfluorobutoxy)-2-hydroxynaphthalene (3.42 g, 10 mmol)was substituted for the 4-benzyloxyphenol, in Example 59,4-benzyloxybenzoic acid (2.28 g, 10 mmol) was substituted for the4-(1,1-dihydroperfluorobutoxy)benzoic acid and1,1-dihydroperfluorobutanol (2.00 g, 10 mmol) was substituted for the4-benzyloxyphenol. The compounds thus-produces were4-(1,1-dihydroperfluorobutoxy)benzoic acid 2'-(6'-benzyloxy)naphthylester (Example 56), S-4-benzyloxyphenyl 4-methylhexanoate (Example 57),4-benzyloxybenzoic acid 2'-[6'-(1,1-dihydroperfluorobutoxy)]naphthylester (Example 58), and 1,1-dihydroperfluorobutyl 4-benzyloxybenzoate(Example 59).

EXAMPLE 60

4-Benzyloxyphenyl 4'-(1,1-dihydroperfluorobutoxy)benzoate (22 g, 0.0438mol) prepared as in Example 55, was dissolved in 50:50 by volumeethanol-ethyl acetate and hydrogenated at 60-65 psig hydrogen pressureover 2.0 g 10% palladium on carbon catalyst at 25° C. for 2 hours. Thereaction solution was filtered to remove the catalyst and the solventwas removed under reduced pressure to yield 17.3 g 4-hydroxyphenyl4'-(1".1"-dihydroperfluorobutoxy)benzoate.

EXAMPLES 61-64

In Examples 61-64, the procedure of Example 60 was followed except the4-benzyloxyphenyl 4'-(1",1"-dihydroperfluorobutoxy)benzoate was not usedand in Example 61 4-(1,1-dihydroperfluorobutoxy)benzoic acid2'-(6'-benzyloxy)naphthyl ester was used, in Example 62S-4-benzyloxyphenyl 4-methylhexanoate was used, in Example 634-benzyloxybenzoic acid 2'-[6'-(1,1-dihydroperfluorobutoxy)]naphthylester was used, and in Example 64, 1,1-dihydroperfluorobutyl4-benzyloxybenzoate was used. The thus-produced compounds were4-(1,1-dihydroperfluorobutoxy)benzoic acid 2'-(6'-hydroxy)naphthyl ester(Example 61), S-4-hydroxyphenyl 4-methylhexanoate (Example 62),4-hydroxybenzoic acid 2'-[6'-(1,1-dihydroperfluorobutoxy)]naphthyl ester(Example 63), and 1,1-dihydroperfluorobutyl 4-hydroxybenzoate (Example64).

EXAMPLE 65

Sodium (0.92 g, 40 mmol) was reacted with 40 ml anhydrous methanol.4-Cyanophenol (4.76 g, 40 mmol) was added to this solution, the methanolwas removed under pressure and the residue was dissolved in 100 ml 3:2by volume toluene-dimethyl formamide. 1,1-Dihydroperfluorooctyltrifluoromethylsulfonate (21.28 g, 40 mmol) was then added dropwise at25° C. and the resulting solution was refluxed for 12 hours. Water (100ml) was added to the reaction mixture and the organic layer was washedwith 10% aqueous sodium hydroxide and then with water. The organic phasewas dried over anhydrous magnesium sulfate, filtered, and concentratedto yield 1-cyano-4-(1,1-dihydroperfluorooctyloxy)benzene.

EXAMPLE 66

1-Cyano-4-(1,1-dihydroperfluorooctyloxy)benzene was dissolved in 50 mlanhydrous ethanol and hydrogen chloride was bubbled through the solutionat 25° C. under a nitrogen atmosphere for 3 hours. The reaction wasallowed to stand for 4 days under nitrogen atmosphere and the resultingprecipitate was quickly collected by filtration and transferred to a 250ml round-bottomed flask containing 20 ml anhydrous ethanol undernitrogen atmosphere. Ammonia (50 ml, 9% in ethanol) was added and thesolution was stirred for 2 days under nitrogen atmosphere. The resultingprecipitated ammonium chloride was removed by filtration and theremaining solution was concentrated under reduced pressure. Theresulting residue was recrystallized from 0.5N aqueoushydrochloride-ethanol to yield 6.15 g4-(1,1-dihydroperfluorooctyloxy)benzamidine hydrochloride.

EXAMPLE 67

Sodium (0.70 g, 30 mmol) was reacted with 20 ml anhydrous methanol andthen S-4-methylhexyl diethylmalonate (2.58 g, 10 mmol) was addedfollowed by the addition of 4-(1,1-dihydroperfluorooctyloxy)benzamidinehydrochloride (5.54 g, 10 mmol). The resulting solution was refluxed for3 days under nitrogen atmosphere, cooled to 25° C. and poured into 6Nhydrochloric acid with stirring. The resulting precipitate was collectedby filtration and dried under vacuum at 80° C. to yield 4.02 gS-2-[4-(1,1-dihydroperfluorooctyloxy)phenyl]-4,6,-dihydroxy-5-(4-methylhexyl)pyrimidine.

EXAMPLE 68

S-2-[4-(1,1-dihydroperfluorooctyloxy)phenyl-4,6,-dihydroxy-5-(4-methylhexyl)pyrimidine(4.00 g, 5.85 mmol) was reacted with 10 ml phosphorous oxychloride and1.5 ml dimethylaniline at reflux under a nitrogen atmosphere for 2 days.The reaction mixture was cooled to 25° C. and the excess phosphorousoxychloride was removed under reduced pressure. The residue was pouredinto a mixture of 4 g sodium hydroxide and 50 g ice with stirring. Thisalkaline solution was extracted 4 times with ethyl ether and thecombined ethereal extracts were washed twice with 6N hydrochloric acid,once with water, dried over anhydrous magnesium sulfate, filtered, andconcentrated under reduced pressure. The resulting crude product waspurified by HPLC using toluene and a silica gel column to yield 1.12 gS-4,6-dichloro-2-[4-(1,1-dihydroperfluorooctyloxy)phenyl-5-(4-methylhexyl)pyrimidine.

EXAMPLE 69

S-4-(2-methylbutyl)-4'-biphenylcarboxylic acid chloride (0.86 g, 3mmol), derived from the carboxylic acid synthesized in Example 52, wasadded to a solution of 4-(1,1-dihydroperfluorohexyloxy)phenol (1.18 g, 3mmol), synthesized in Example 22, in 30 ml dry ethyl ether containing 1ml of dry triethylamine was added. The reaction was stirred for 1 day atroom temperature at which time it was filtered, washed once with 0.5MHCl, once with water, dried over anhydrous magnesium sulfate, filtered,and concentrated under reduced pressure. The crude product was purifiedby HPLC (toluene, silica gel) followed by recrystallization fromanhydrous ethanol to produce Compound 1, Table I,S-4-(2-methylbutyl)-4'-biphenylcarboxylic acidp'-(1,1-dihydroperfluorohexyloxy)phenyl ester (0.98 g, 51% yield). Thestructure was confirmed by H- and F-NMR, MS, and IR.

EXAMPLES 70-73

In Examples 70-73, compounds 2-5 of Table I were prepared as in Example69 except that the precursor compounds indicated below were substitutedfor the S-2-(2-methylbutyl)-4'-biphenylcarboxylic acid chloride and the4-(1,1-dihydroperfluorohexyloxy)phenol.

    ______________________________________                                               Com-                                                                   Example                                                                              pound     Precursors                                                   ______________________________________                                        70     2         S-4-(2-methylbutyl)-4'-biphenyl carboxylic                                    acid (Example 52) and                                                         4-(1,1-dihydroperfluorobutyloxy)phenol                                        (Example 21)                                                 71     3         S-4-(2-methylbutyl)-4'-biphenyl carboxylic                                    acid (Example 52) and                                                         4-(1,1-dihydroperfluorooctyloxy)phenol                                        (Example 23)                                                 72     4         S-4-(2-methylbutyloxy)-4'-biphenyl                                            carboxylic acid (Example 53) and                                              1,1-dihydroperfluorooctanol                                  73     5         S-4-(2-methylbutyl)-4'-biphenyl carboxylic                                    acid (Example 52) and                                                         1,1-dihydroperfluorooctanol                                  ______________________________________                                    

EXAMPLE 74

To a solution of S-4-(4-methylhexyloxy)thiophenol (1.12 g, 5 mmol),synthesized in Example 31 in 30 ml anhydrous ethyl ether containing 1 mlof dry triethylamine, 4-(1,1-dihydroperfluorohexyloxy)benzoic acidchloride (2.20 g, 5 mmol), derived from the material synthesized inExample 9, was added dropwise. The reaction was stirred for 1 day atroom temperature at which time it was filtered, washed once with 0.5MHCl, washed once with water, dried over anhydrous magnesium sulfate,filtered, and concentrated under reduced pressure. The crude product waspurified by HPLC (toluene, silica gel) followed by recrystallizationfrom anhydrous ethanol to produce Compound 6 of Table I,S-4-(1,1-dihydroperfluorohexyloxy)thiolbenzoic acidp'-(4-methylhexyloxy)phenyl ester (2.55 g, 81% yield). The structure wasconfirmed by H- and F-NMR, MS, and IR.

EXAMPLES 75-80

In Examples 75-80, compounds 7-12 of Table I were prepared as in Example74 except that the precursor compounds indicated below were substitutedfor the S-4-(4-methylhexyloxy)thiophenol and the4-(1,1-dihydroperfluorohexyloxy)benzoic acid chloride.

    ______________________________________                                               Com-                                                                   Example                                                                              pound   Precursors                                                     ______________________________________                                        75      7      S-4-(2-methylbutyloxy)thiophenol (Example                                     32) and                                                                       4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               76      8      S-4-(4-methylhexyloxy)thiophenol (Example                                     31) and                                                                       4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               77      9      S-4-(2-methylbutyloxy)thiophenol (Example                                     32) and                                                                       4-(1,1-dihydroperfluooctyloxy)benzoic acid                                    (Example 10)                                                   78     10      S-4-(4-methylhexyloxy)thiophenol (Example                                     31) and                                                                       4-(1,1-dihydroperfluooctyloxy)benzoic acid                                    (Example 10)                                                   79     11      S-4-(2-methylbutyloxy)thiophenol (Example                                     32) and                                                                       4-(1,1-dihydroperfluorohexyloxy)benzoic                                       acid (Example 9)                                               80     12      S-4-(2-methylbutyl)thiophenol (Example 34)                                    and                                                                           4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               ______________________________________                                    

EXAMPLE 81

S-4-(4-methylhexyloxy)benzoic acid (2.36 g, 10 mmol), synthesized inExample 1, and 4-(1,1-dihydroperfluorobutyloxy)phenol (2.92 g, 10 mmol),synthesized in Example 21, were dissolved in 50 ml methylene chloride.6-(N,N-Dimethylamino)pyridine (0.1 g) was added to the reaction followedby N,N'-dicyclohexylcarbodiimide (2.27 g, 11 mmol). The reaction wasstirred at room temperature under nitrogen atmosphere for 1 day. Thereaction was filtered and washed successively with 0.5M HCl, 5% sodiumbicarbonate, and water. The organic layer was dried over magnesiumsulfate, filtered, and concentrated under reduced pressure. The crudematerial was purified by HPLC (toluene, silica gel) followed byrecrystallization from ethanol to produce Compound 13 of Table I,S-4-(4-methylhexyloxy)benzoic acidp'-(1,1-dihydroperfluorobutyloxy)phenyl ester (3.84 g, 75% yield). Thestructure was confirmed by H- and F-NMR, MS, and IR.

EXAMPLES 82-114

In Examples 82-114, compounds 14-46 of Table I were prepared as inExample 81 except that the precursor compounds indicated below weresubstituted for the S-4-(4-methylhexyloxy)benzoic acid and the4-(1,1dihydroperfluorobutyloxy)phenol.

    ______________________________________                                               Com-                                                                   Example                                                                              pound   Precursors                                                     ______________________________________                                        82     14      S-4-(4-methylhexyloxy)benzoic acid                                            (Example 1) and                                                               1-(4-hydroxyphenoxy)-2-(1,1-dihydroper-                                       fluorooctyloxy)ethane (Example 27)                             83     15      S-4-(2-methylbutoxy)phenol (Example 17)                                       and                                                                           4-(1,1-dihydroperfluorohexyloxy)benzoic                                       acid (Example 9)                                               84     16      S-4-(2-methylbutoxy)phenol (Example 17)                                       and 4-(1,1-dihydroperfluoroctyloxy)benzoic                                    acid (Example 10)                                              85     17      S-4-(4-methylhexyloxy)phenol (Example 16)                                     and                                                                           4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               86     18      S-4-(4-methylhexyloxy)phenol (Example 16)                                     and                                                                           4-(1,1-dihydroperfluorohexyloxy)benzoic                                       acid (Example 9)                                               87     19      S-4(-methylhexyloxy)phenol (Example 16)                                       and 4-(1,1-dihydroperfluorooctyloxy                                           benzoic acid (Example 10)                                      88     20      S-2-methylbutyl 4-hydroxybenzoate                                             and                                                                           4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               89     21      S-4-(4-methylhexyloxy)benzoic acid                                            (Example 1) and                                                               4-(1,1-dihydroperfluorohexyloxy)phenol                                        (Example 22)                                                   90     22      S-4-(4-methylhexloxy)benzoic acid (Example                                    1) and                                                                        4-(1,1-dihydroperfluorooctyloxy)phenol                                        (Example 23)                                                   91     23      S-4-(4-methylhexyloxy)benzoic acid                                            (Example 1) and                                                               4-(1,1,2,2-tetrahydroperfluorohexyloxy)-                                      phenol (Example 24)                                            92     24      S-4-(4-methylhexyloxy)benzoic acid                                            (Example 1) and                                                               4-(1,1,7-trihydroperfluoroheptyloxy)phenol                                    (Example 25)                                                   93     25      S-4-(2-methylbutyloxy)benzoic acid                                            (Example 2) and                                                               4-(1,1-dihydroperfluorooctyloxy)phenol                                        (Example 23)                                                   94     26      S-4-(2-methylbutyl)phenol and                                                 4-(1,1-dihydroperfluorohexyloxy)benzoic                                       acid (Example 9)                                               95     27      S-4-(2-methylbutyloxy)benzoic acid                                            (Example 2) and                                                               4-(1,1-dihydroperfluorohexyloxy)phenol                                        (Example 22)                                                   96     28      S-α-(2-methylbutyloxy)toluic acid (Example                              7) and                                                                        4-(1,1-dihydroperfluorooctyloxy)phenol                                        (Example 23)                                                   97     29      S-4-(2-methylbutyloxy)phenol (Example 17)                                     and                                                                           4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               98     30      S-4-(4-methylhexyloxy)benzoic acid (Example                                   1) and                                                                        1-(4-hydroxyphenoxy)-11-perfluorooctyl-                                       undecane (Example 18)                                          99     31      S-3-chloro-4-(4-methylhexyloxy)benzoic                                        acid (Example 3) and                                                          4-(1,1-dihydroperfluorobutyloxy)phenol                                        (Example 21)                                                   100    32      S-3-chloro-4-(4-methylhexyloxy)benzoic                                        acid (Example 3) and                                                          4-(1,1-dihydroperfluorohexyloxy)phenol                                        (Example 22)                                                   101    33      S-4-(4-methylhexyloxy)phenol (Example 16                                      and                                                                           3-chloro-4-(1,1-dihydroperfluorohexyloxy)-                                    benzoic acid (Example 12)                                      102    34      S-3-methoxy-4-(4-methylhexyloxy)benzoic                                       acid (Example 4) and                                                          4-(1,1-dihydroperfluorobutyloxy)phenol                                        (Example 21)                                                   103    35      S-3-methoxy-4-methylhexyloxy)benzoic acid                                     (Example 4) and                                                               4-(1,1-dihydroperfluorohexyloxy)phenol                                        (Example 22)                                                   104    36      S-4-(4-methylhexyloxy)phenol (Example 16)                                     and                                                                           3-methoxy-4-(1,1-dihydroperfluorohexyloxy)                                    benzoic acid (Example 13)                                      105    37      S-4-(4-methylhexyloxy)benzoic acid                                            (Example 1) and                                                               N-ethyl-N-[2-(4-hydroxyphenoxy)ethyl]                                         perfluorooctylsulfonamide (Example 19)                         106    38      S-4-(4-methylhexyloxy)benzoic acid                                            (Example 1) and                                                               4-(1,1,11-trihydroperfluoroundecyloxy)-                                       phenol (Example 26)                                            107    39      S-4-(4-methylhexyloxy)phenol (Example 16)                                     and 4-(1,1,7-trihydroperfluoroheptyloxy)-                                     benzoic acid (Example 11)                                      108    40      S-4-(4-methylhexyloxy)benzoic acid                                            (Example 1) and                                                               4-(1,1-dihydroperfluoroethoxy)phenol                                          (Example 28).                                                  109    41      S-4-)1-methylheptyloxy)benzoic acid                                           (Example 6) and                                                               4-(1,1-dihydroperfluorobutyloxy)phenol                                        (Example 21)                                                   110    42      S-4-)1-methylheptyloxy)benzoic acid                                           (Example 6) and                                                               4-(1,1-dihydroperfluorohexyloxy)phenol                                        (Example 22)                                                   111    43      S-4-)1-methylheptyloxy)benzoic acid                                           (Example 6) and                                                               4-(1,1-dihydroperfluorooctyloxy)phenol                                        (Example 23)                                                   112    44      S-4-(4-methylhexyloxy)phenol (Example 16)                                     and                                                                           2-chloro-4-(1,1-dihydroperfluorobutyloxy)-                                    benzoic acid (Example 14)                                      113    45      S-4-(4-methylhexyloxy)phenol (Example 16)                                     and                                                                           2-chloro-4-(1,1-dihydroperfluorooctyloxy)-                                    benzoic acid (Example 15)                                      114    46      S-4-(1-methylheptyloxy)phenol (Example 20)                                    and                                                                           4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               ______________________________________                                    

EXAMPLE 115

S-6-(4-methylhexyloxy)-3-pyridinecarboxylic acid (2.37 g, 10 mmol),synthesized in Example 48, and 4-(1,1-dihydroperfluorohexyloxy)phenol(3.92 g, 10 mmol), synthesized in Example 22, were dissolved in 50 mlmethylene chloride. 4-(N,N-Dimethylamino)pyridine (0.1 g) was added tothe reaction followed by N,N'-dicyclohexylcarbodiimide (2.27 g, 11mmol). The reaction material was refluxed under a nitrogen atmospherefor 1 day. The reaction mixture was filtered and washed successivelywith 0.5M HCl, 5% sodium bicarbonate, and water. The organic layer wasdried over magnesium sulfate, filtered, and concentrated under reducedpressure. The crude material was purified by HPLC (toluene, silica gel)followed by recrystallization from heptane to produce Compound 47 ofTable I, S-6-(4-methylhexyloxy)-3-pyridinecarboxylic acidp'-(1,1-dihydroperfluorohexyloxy)phenyl ester (2.90 g, 47% yield). Thestructure was confirmed by H- and F-NMR, MS, and IR.

EXAMPLES 116-121

In Examples 116-121, compounds 48-53 of Table I were prepared as inExample 115 except that the precursor compounds indicated below weresubstituted for the S-6-(4-methylhexyloxy)-3-pyridinecarboxylic acid andthe 4-(1,1-dihydroperfluorohexyloxy)phenol.

    ______________________________________                                               Com-                                                                   Example                                                                              pound   Precursor                                                      ______________________________________                                        116    48      S-4-(4-methylhexyloxy)phenol (Example 16)                                     and                                                                           6-(1,1-dihydroperfluorobutyloxy)-3-                                           pyridinecarboxylic acid (Example 51)                           117    49      S-6-(4-methylhexyloxy)-3-pyridine                                             carboxylic acid (Example 48) and                                              4-(1,1-dihydroperfluorooctyloxy)phenol                                        (Example 23)                                                   118    50      S-6-(2-methylbutyloxy)-3-pyridine-                                            carboxylic acid (Example 49) and                                              4-(1,1-dihydroperfluorohexyloxy)phenol                                        (Example 22)                                                   119    51      S-6-(4-methylhexyloxy)-3-pyridine-                                            carboxylic acid (Example 48) and                                              4-(1,1-dihydroperfluorobutyloxy)phenol                                        (Example 21)                                                   120    52      S-6-(1-methylheptyloxy)-3-pyridine-                                           carboxylic acid (Example 50) and                                              4-(1,1-dihydroperfluorobutyloxy)phenol                                        (Example 21)                                                   121    53      S-4-(4-methylhexyloxy)thiophenol (Example                                     31) and                                                                       6-(1,1-dihydroperfluorobutyloxy)-                                             3-pyridinecarboxylic acid (Example 51)                         ______________________________________                                    

EXAMPLE 122

S-4-(4-methylhexyloxy)benzoic acid (0.71 g, 3 mmol), synthesized inExample 1, and 6-(1,1-dihydroperfluorobutyloxy)-2-napthol (1.03 g, 3mmol), synthesized in Example 42, were dissolved in 50 ml methylenechloride. 4-(N,N-Dimethylamino)pyridine (0.03 g) was added to thereaction followed by N,N'-dicyclohexylcarbodiimide (1.03 g, 5 mmol). Thereaction was stirred at room temperature under nitrogen atmosphere for 1day. The reaction was filtered and washed successively with 0.5M HCl, 5%sodium bicarbonate, and water. The organic layer was dried overanhydrous magnesium sulfate, filtered, and concentrated under reducedpressure. The crude material was purified by HPLC (toluene, silica gel)followed by recrystallization from heptane to provide Compound 54 ofTable I, S-4-(4-methylhexyloxy)benzoic acid2'-(6'-(1,1-dihydroperfluorobutyloxy))naphthyl ester (0.60 g, 36%yield). The structure was confirmed by H- and F-NMR, MS, and IR.

EXAMPLES 123-128

In Examples 123-128 compounds 55-60 of Table I were prepared as inExample 122 except that the precursor compounds indicated below weresubstituted for S-6-(4-methylhexyloxy)benzoic acid and the6-(1,1-dihydrofluorobutyloxy)-2-naphthol.

    ______________________________________                                               Com-                                                                   Example                                                                              pound   Precursor                                                      ______________________________________                                        123    55      S-4-(4-methylhexyloxy)benzoic acid                                            (Example 1) and                                                               7-(1,1-dihydroperfluorobutyloxy)-2-                                           naphthol (Example 45)                                          124    56      S-6-(4-methylhexyloxy)-2-naphthol (Example                                    38 and                                                                        4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               125    57      S-6-(4-methylhexyloxy)-2-naphthol (Example                                    38) and                                                                       4-(1,1-dihydroperfluorohexyloxy)benzoic                                       acid (Example 9)                                               126    58      S-4-(4-methylhexyloxy)-1-naphthol (Example                                    39) and                                                                       4-(1,1-dihydroperfluorobutyloxy)benzoic                                       acid (Example 8)                                               127    59      S-5-(4-methylhexyloxy)-1-naphthol (Example                                    40) and                                                                       4-(1,1-dihydroperfluorohexyloxy)benzoic                                       acid (Example 9)                                               128    60      S-3-methoxy-4-(4-methylhexyloxy)benzoic                                       acid (Example 4) and                                                          6-(1,1-dihydroperfluorobutyloxy)-2-                                           naphthol (Example 42)                                          ______________________________________                                    

EXAMPLE 129

4-(1,1-Dihydroperfluorohexyloxy)benzaldehyde (2.02 g, 5 mmol),synthesized in Example 35, and S-4-(2-methylbutyl)aniline (0.82 g, 5mmol) which was prepared as described in U.S. Pat. No. 4,394,070, whichis incorporated herein by reference for that purpose, were dissolved inanhydrous ethanol and 1 drop of glacial acetic acid was added. Themixture was brought to reflux for 4 hours and allowed to cool to roomtemperature. The resulting product crystallized out of solution and wascollected by filtration to provide compound 61 of Table 1,S-4-(1,1-dihydroperfluorohexyloxy)benzylidene-p'-(2-methyl-butyl)aniline,(1.51 g, 55% yield). The structure was confirmed by H- and F-NMR, MS,and IR.

EXAMPLE 130

In Example 130 compound 62 of Table I was prepared as in Example 129except that S-2-methylbutyl 4-aminobenzoate, the preparation of which isdisclosed in European Patent Application No. 0,163,229 which isincorporated herein for that purpose, was substituted for theS-4-(2-methylbutylaniline).

EXAMPLE 131

S-4-(2'-Methylbutoxy)selenophenol (1.21 g, 0.005 mol) prepared as inExample 33, 4-(1',1'-dihydroperfluorobutoxy)benzoic acid (1.60 g, 0.005mol), and 4-dimethylaminopyridine (0.05 g) were dissolved in 50 mlmethylene chloride and to this solution was addeddicyclohexylcarbodiimide (1.03 g, 0.005 mol). This reaction mixture wasrefluxed for 2 days under a nitrogen atmosphere. The reaction productwas cooled to 25° C., filtered, washed sequentially with 0.5Nhydrochloric acid, 5% aqueous sodium bicarbonate, and water, dried overanhydrous magnesium sulfate, filtered, and concentrated. Thisconcentrate was purified by HPLC using toluene and a silica gel columnto yield 0.3 g S-4-(2'-methylbutoxy)phenyl4"(1"',1"'-dihydroperfluorobutoxy)selenobenzoate (Compound 63).

EXAMPLE 132

1,1-Dihydroperfluorobutanol (2.00 g, 0.01 mol) was added to a stirredsuspension of sodium hydride (0.40 g, 0.01 mol, 60% in mineral oil) in20 ml benzene at 25° C. under a nitrogen atmosphere and the resultingmixture was stirred at 25° C. for 30 minutes. To this mixtureS-3-chloro-6-[4'-(4"-methylhexyloxy)phenoxy]pyridizine (3.2 g, 0.01mol), prepared as in Example 54, in 30 ml benzene was added dropwise at25° C. under a nitrogen atmosphere. After this addition, the reactionmixture was refluxed for 2 hours and then cooled to 25° C. Toluene (50ml) was added to the cooled reaction product which was then washed threetimes with water, dried over anhydrous magnesium sulfate, filtered, andconcentrated. This concentrate was purified by HPLC using a silicacolumn and toluene as eluent, followed by recrystallization from ethanolto yield Compound 64,S-3-(1',1'-dihydroperfluorobutoxy)-[4"-(methylhexyloxy)phenoxylpyridizine.

EXAMPLE 133

4-Hydroxyphenyl 4'-(1,1,-dihydroperfluorobutoxy)benzoate (2.06 g, 5mmol), prepared as in Example 60. S-2-chloro-4-methylpentanoic acid(0.75 g, 5 mmol), and 4-dimethylaminopyridine (0.05 g) were dissolved in50 ml methylene chloride. Dicyclohexylcarbodiimide (1.24 g, 6 mmol) wasthen added in a single portion. This reaction mixture was stirred at 25°C. under a nitrogen atmosphere for 12 hours. The reaction was filteredand then washed sequentially with 0.5N hydrochloric acid, 5% sodiumbicarbonate, and water, dried over anhydrous magnesium sulfate,filtered, and concentrated. This concentrate was recrystallized fromethanol to yield 1.82 g S-4-(2'-chloro-4'-methylpentanoyloxy)phenyl4"-(1,1-dihydroperfluorobutxoy)benzoate (Compound 65).

EXAMPLES 134-138

In Examples 134-138 compounds 66-70 of Table I were prepared as inExample 133 except that the precursor compounds set forth below weresubstituted for the 4-hydroxyphenyl4'-(1,1-dihydroperfluorobutoxy)benzoate in Examples 134-136 and theprecursor compounds set forth below were substituted for the4-hydroxyphenyl 4'-(1,1-dihydroperfluorobutoxy)benzoate and theS-2-chloro-4-methylpentanoic acid in Examples 137-138.

    ______________________________________                                        Example                                                                              Compound  Precursors                                                   ______________________________________                                        134    66        4-(1,1-dihydroperfluorobutoxy)benzoic                                         acid                                                                          2'-(6'-hydroxy)naphthyl ester (Example                                        61)                                                          135    67        4-hydroxybenzoic acid                                                         2'-[6'-(1,1-dihydroperfluoro-                                                 butoxy)]naphthyl ester (Example 63)                          136    68        4-(1,1-dihydroperfluorobutyloxy)                                              4'-hydroxybiphenyl (Example 46)                              137    69        S-4-hydroxyphenyl 4-methylhexanoate                                           (Example 62) and                                                              4-(1,1-dihydroperfluorobutoxy)benzoic                                         acid (Example 8)                                             138    70        1,1-dihydroperfluorobutyl                                                     4'-hydroxybenzoate (Example 64) and                                           S-4-(methylhexyloxy) benzoic acid                                             (Example 1)                                                  ______________________________________                                    

EXAMPLE 139

S-4,6-Dichloro-2-[4'-(1",1"-dihydroperfluorooctyloxy)phenyl]-5-(4-ethylhexyl)pyrimidine(100 mg, 0.14 mmol) was dissolved in 100 ml 1:1 by volume ethanol-ethylacetate, 2 ml 1N sodium hydroxide was added, and the mixture washydrogenated over 0.3 g 10% palladium on carbon catalyst at 60 psighydrogen pressure for 30 minutes. The catalyst was removed by filtrationand the filtrate was concentrated. This concentrate was dissolved indichloromethane, dried over anhydrous magnesium sulfate, filtered, andconcentrated to yield Compound 71,2-[4-(1.1-dihydroperfluorooctyloxy)phenyl]-5-(4-methylhexyl)pyrimidine.

                                      TABLE I                                     __________________________________________________________________________    No.                                                                              Compound                                                                   __________________________________________________________________________     1                                                                                ##STR24##                                                                  2                                                                                ##STR25##                                                                  3                                                                                ##STR26##                                                                  4                                                                                ##STR27##                                                                  5                                                                                ##STR28##                                                                  6                                                                                ##STR29##                                                                  7                                                                                ##STR30##                                                                  8                                                                                ##STR31##                                                                  9                                                                                ##STR32##                                                                 10                                                                                ##STR33##                                                                 11                                                                                ##STR34##                                                                 12                                                                                ##STR35##                                                                 13                                                                                ##STR36##                                                                 14                                                                                ##STR37##                                                                 15                                                                                ##STR38##                                                                 16                                                                                ##STR39##                                                                 17                                                                                ##STR40##                                                                 18                                                                                ##STR41##                                                                 19                                                                                ##STR42##                                                                 20                                                                                ##STR43##                                                                 21                                                                                ##STR44##                                                                 22                                                                                ##STR45##                                                                 23                                                                                ##STR46##                                                                 24                                                                                ##STR47##                                                                 25                                                                                ##STR48##                                                                 26                                                                                ##STR49##                                                                 27                                                                                ##STR50##                                                                 28                                                                                ##STR51##                                                                 29                                                                                ##STR52##                                                                 30                                                                                ##STR53##                                                                 31                                                                                ##STR54##                                                                 32                                                                                ##STR55##                                                                 33                                                                                ##STR56##                                                                 34                                                                                ##STR57##                                                                 35                                                                                ##STR58##                                                                 36                                                                                ##STR59##                                                                 37                                                                                ##STR60##                                                                 38                                                                                ##STR61##                                                                 39                                                                                ##STR62##                                                                 40                                                                                ##STR63##                                                                 41                                                                                ##STR64##                                                                 42                                                                                ##STR65##                                                                 43                                                                                ##STR66##                                                                 44                                                                                ##STR67##                                                                 45                                                                                ##STR68##                                                                 46                                                                                ##STR69##                                                                 47                                                                                ##STR70##                                                                 48                                                                                ##STR71##                                                                 49                                                                                ##STR72##                                                                 50                                                                                ##STR73##                                                                 51                                                                                ##STR74##                                                                 52                                                                                ##STR75##                                                                 53                                                                                ##STR76##                                                                 54                                                                                ##STR77##                                                                 55                                                                                ##STR78##                                                                 56                                                                                ##STR79##                                                                 57                                                                                ##STR80##                                                                 58                                                                                ##STR81##                                                                 59                                                                                ##STR82##                                                                 60                                                                                ##STR83##                                                                 61                                                                                ##STR84##                                                                 62                                                                                ##STR85##                                                                 63                                                                                ##STR86##                                                                 64                                                                                ##STR87##                                                                 65                                                                                ##STR88##                                                                 66                                                                                ##STR89##                                                                 67                                                                                ##STR90##                                                                 68                                                                                ##STR91##                                                                 69                                                                                ##STR92##                                                                 70                                                                                ##STR93##                                                                 71                                                                                ##STR94##                                                                 __________________________________________________________________________

Compounds in Table I were evaluated for transition temperatures,birefrigence, and pitch length using the following procedures:

Transition temperature determinations were made either by opticalobservation of material phase changes using a Mettler FP-5 hot stage anda Leitz polarizing microscope, or by standard practice differentialscanning calorimetry (DSC) using a Perkin Elmer model DSC-4.

Birefringence of the C* phase was measured using a wedged technique asdescribed in Japanese Journal of Applied Physics, Vol. 24, No. 11, Nov.1985, p. 1389-1393.

Pitch length was measured by optical microscopy as described in Journalde Physique Colloq., Vol. 37, 1976, p. C3-129-132, except that 50-75micron thick cells were used.

Transition temperatures, birefrigence and pitch length are reported inTable II.

Where the material melts during the K→I transition, the notation "mp"for melting point follows the melt temperature. Birefrigence and pitchlength measurements are not reported in Table II for materials thateither do not show a chiral smectic C phase themselves or whose phase isobserved only upon rapid cooling and therefore cannot be measured.

                                      TABLE II                                    __________________________________________________________________________    Transition Temp (°C.)                                                                             Birefringence                                                                        Pitch length                                Cmpd                                                                              I→A                                                                           A→C*                                                                           C*→K                                                                           (Δn)                                                                           (microns)                                   __________________________________________________________________________     1  210    82           78 --     --                                           2  188    100          94 .16 (98° C.)                                                                  5.7                                          3  231    --      (A→K)                                                                       93 --     --                                           4  115    96 (H*)      -- --     --                                           5  101            (A→K)                                                                       72 --     --                                           6  108    93           49 .12 (81° C.)                                                                  5.1                                          7  82     76           71 .14 (75° C.)                                                                  3.0                                          8  86     60           -- .13 (54° C.)                                                                  3.3                                          9  125    --      (A→K)                                                                       97 --     --                                          10  132    95           74 .09 (82° C.)                                                                  13.9                                        11  98     85           63 .12 (78° C.)                                                                  7.0                                         12  68 mp  --           -- --     --                                          13  76     60           40 .12 (56° C.)                                                                  6.0                                         14  91     72           51 --     --                                          15  83     61           -- .10 (58° C.)                                                                  6.6                                         16  110    81           66 --     --                                          17  74     60           57 --     --                                          18  89     78           52 .11 (55° C.)                                                                  6.0                                         19  109    81           78 .09 (79° C.)                                                                  6.7                                         20  101                                                                              mp  --           -- --     --                                          21  96     62           23.sup.a                                                                         .11 (53° C.)                                                                  7.4                                         22  124    65           54.sup.b                                                                         .10 (59° C.)                                                                  9.8                                         23  104    75           47 .10 (73° C.)                                                                  7.3                                         24  48     --      (A→K)                                                                       30 --     --                                          25  116    --      (A→K)                                                                       51 --     --                                          26  68 mp  --           -- --     --                                          27  85     --      (A→K)                                                                       40 --     --                                          28  78     --      (A→K)                                                                       53 --     --                                          29  86 mp  --           -- --     --                                          30  122    90           85 .07 (99° C.)                                                                  20.0                                        31  57     --      (A→K)                                                                       55 --     --                                          32  84     --      (A→K)                                                                       28 --     --                                          33  63     41           35 .08 (40° C.)                                                                  2.0                                         34  70 mp  --           -- --     --                                          35  59     --      (A→K)                                                                       40 --     --                                          36  42     --      (A→K)                                                                       28 --     --                                          37  113    --      (A→K)                                                                       78 --     --                                          38  97     --      (A→K)                                                                       91 --     --                                          39  61 mp  --           -- --     --                                          40  69     --      (A→K)                                                                       35 --     --                                          41  41 mp  --           -- --     --                                          42  18 (I→K)                                                                      --           -- --     --                                          43  40     21 (A→H*)                                                                           -- --     --                                          44  liquid --           -- --     --                                          45  71     --      (A→K)                                                                       37 --     --                                          46  37 mp  --              --     --                                          47  62     33           -- .10 (31° C.)                                                                  5.8                                         48  49     28           22 --     --                                          49  88     54           51 --     --                                          50  54 mp  --           -- --     --                                          51  48     --      (A→K)                                                                       30 --     --                                          52  35 mp  --           -- --     --                                          53  75     32           28 --     --                                          54  124    83           69 .14 (80° C.)                                                                  6.6                                         55  98 mp  --           -- --     --                                          56  119    62           47 .14 (58° C.)                                                                  4.2                                         57  151    96           63 .12 (94° C.)                                                                  6.9                                         58  85 mp  --           -- --     --                                          59  80     37              .06 (36°  C.)                                                                 6.0                                         60  93 mp  --           -- --     --                                          61  76     --      (A→K)                                                                       60 --     --                                          62  118    --      (A→K)                                                                       83 --     --                                          63  73     --      (A→K)                                                                       66                                                    64  68 (I→K                                                                       --           -- --     --                                          65  41     --      (A→K)                                                                       40 --     --                                          66  131    --      (A→K)                                                                       125                                                                              --     --                                          67  110    --      (A→K)                                                                       90 --     --                                          68  98     --      (A→K)                                                                       88 --     --                                          69  86     72           65                                                    70  70     60           25                                                    71  72 mp  --           -- --     --                                          __________________________________________________________________________     .sup.a on cooling an additional peak was observed by DSC at 25° C.     .sup.b on cooling an additional peak was observed by DSC at 56° C.

EXAMPLES 140-168

Binary mixtures were made of compounds which of themselves did notexhibit a chiral smectic mesophase. Equal weight amounts of materialswere placed next to each other on a clean glass microscope slide andcovered with a clean glass cover slip. This preparation was warmed overa bunsen burner until both materials were isotropic at which point acontinuous composition gradient was formed between the two components.The slide was then placed on a microscope between crossed polarizers,allowed to cool, and the mesophases present were identified. Thecompounds mixed as components 1 and 2 of the binary mixtures and theobserved mesophases are set forth in Table III.

                  TABLE III                                                       ______________________________________                                               Compound No.  Compound No.  Observed                                   Example                                                                              for Component 1                                                                             for Component 2                                                                             mesophases                                 ______________________________________                                        140    20            29            A,C*                                       141    27            29            A,C*                                       142    20            27            A,C*                                       143    27            50            A,C*                                       144    50            51            A,C*                                       145    20            26            A,C*                                       146    25            28            A,H*                                       147    20            24            A,C*                                       148    27            24            A,C*                                       149    36            37            A,C*                                       150    55            32            A,C*                                       151    29            32            A,C*,H*                                    152    30            36            A,C*                                       153    34            36            A,C*                                       154    35            61            A,C*                                       155    34            62            A,C*                                       156    50            52            A,C*                                       157    29            31            A,C*                                       158    12            20            A,C*                                       159    24            40            A,C*                                       160    71            20            A,H*                                       161    41            37            A,H*                                       162    43            32            A,C*,H*                                    163    44            32            A,C*                                       164    45            32            A,C*                                       165    42            51            A,C*                                       166    63            27            A,C*                                       167    46            51            A,C*                                       168    68            20            A,C*                                       ______________________________________                                    

EXAMPLE 169

Admixtures of Compound No. 20 and Compound No. 29 were prepared atvarious mixing ratios as set forth in Table IV. Transition temperaturesfor the admixtures, as well as for each individual compound are setforth in Table IV.

                  TABLE IV                                                        ______________________________________                                        Compound 20                                                                             Compound 29 Transition temperature (°C.)                     (wt %)    (wt %)      I→A                                                                           A→C*                                                                         C→K*                                                                         I→K                           ______________________________________                                        100        0          --     --    --    88                                   59        41          64.9   58.5  56.3                                       49        51          64.3   57.5  56.3                                       39        61          63.6   62.7  62.3                                        0        100         --     --    --    79                                   ______________________________________                                    

EXAMPLE 170

A device utilizing ferroelectric liquid crystal materials of thisinvention was constructed as follows. A 600 Å thick indium tin oxidepattern of 25 lines, 700 micrometers wide and spaced 300 micrometersapart, was deposited on two 60 mm by 70mm Corning 7104 glass plates.

One plate was further coated with photoresist, exposed through acircular holed mask and developed resulting in photoresist postsapproximately 1.7 microns in height, 200 microns in diameter and spaced5 mm apart. These posts serve as spacers for the assembled devicedetermining the liquid crystal fill gap between the plates.

Both plates were further coated with DuPont VK6300 polyimide andundirectionally buffed with a buffing pad, imparting order to thepolymer layer which then serves to uniaxially align the enclosed liquidcrystal.

The line patterns of the two plates were then aligned 90° to each otherforming a 25×25 pixel array. The plates were sealed around their edgeswith Norland UV sealant #UVS-91. This construction was then filled in avacuum chamber with the following mixture:

23.3% of compound number 13,

27.4% of compound number 21,

46.1% of S-2-methylbutyl-4-(4'-octyloxybenzoyloxy)benzoate, and

3.2% of S-4-hexyloxyphenyl-4'-[4"(4"'methylhexyloxy)benzoyloxy]benzoate.

The last two compounds are described in "Some Novel FerroelectricSmectic Liquid Crystals" by J. W. Goodby and T. M. Leslie in "LiquidCrystals and Ordered Fluids Vol. 4, pp 1-42, edited b A. C. Griffin andJ. F. Johnson. The mixture, when evaluated at room temperature had apitch length of 3.0-4.0 microns, a tilt angle of 27°, and abirefringence of 0.15, transition temperatures for phase changes were76° C.(I→A) and 45° C.(A→C*).

The filled device was heated to 74° C. to the isotropic phase of theliquid crystal mixture and allowed to cool. As the material cooled fromits isotropic phase to its A phase, the molecules were spontaneouslyoriented by the buffed polymer surfaces. The liquid crystal maintainsthis alignment on further cooling to room temperature.

Electrical driving circuitry was connected to the indium tin oxidelines. Application of ±40 volts across any pixel resulted in the liquidcrystal mixture switching with a response time of 110 microseconds.

EXAMPLE 171

A mixture of ferroelectric liquid crystal compounds was prepared using

    ______________________________________                                        S-4-(4-methylhexyloxy)benzoic acid                                                                    30 wt. %                                              p'-(1,1-dihydroperfluorobutyloxy)-                                            phenyl ester (Compound 13)                                                    S-4-(4-methylhexyloxy)benzoic acid                                                                    19 wt. %                                              p'-(1,1-dihydroperfluorohexyloxy)-                                            phenyl ester (Compound 21)                                                    S-4-(2'-chloro-4'-methylpentanoyloxy)-                                                                11 wt. %                                              phenyl 4"-(1,1-dihydroperfluorobutoxy)-                                       benzoate (Compound 65)                                                        S-2-methylbutyl 4-(4'-octyloxybenzoyl-                                                                40 wt %                                               oxy)benzoate (Goodby and Leslie, supra)                                       ______________________________________                                    

The transition temperatures for the mixture were

I→A 69° C.

A→C* 49° C.

C*→K 0° C.

A device prepared as in Example 170, was vacuum filled as in Example170. The response time was measured at the rising edge of the cellphotoresponse and calculated from 10-90% of the maximum transmission.The response time, measured at a voltage of ±30 and a temperature of 23°C., was 69 μs. The polarization, determined at 23° C. according to theprocedure of Miyasato et al., Jap. J. Appl. Phys., 22, 1983, p. 661, was22 nC/cm².

EXAMPLES 172-175

For Examples 172-175, ferroelectric liquid crystal mixtures wereprepared and tested as in Example 171. The mixtures, as well as thetransition temperatures, response times and polarization for themixtures, were as follows:

EXAMPLE 172

    ______________________________________                                        S-4-(4-methylhexyloxy)benzoic acid                                                                    31 wt. %                                              p'-(1,1-dihydroperfluorobutyloxy)-                                            phenyl ester (Compound 13)                                                    S-4-(4-methylhexyloxy)benzoic acid                                                                    19 wt. %                                              p'-(1,1-dihydroperfluorohexyloxy)-                                            phenyl ester (Compound 21)                                                    S-4-(2'-chloro-4'-methylpentanoyloxy)-                                                                20 wt. %                                              phenyl 4"-(1,1-dihydroperfluorobutoxy)-                                       benzoate (Compound 65)                                                        S-2-methylbutyl-4-(4'-octyloxybenzoyl-                                                                30 wt %                                               oxy)benzoate (Goodby and Leslie, supra)                                       ______________________________________                                    

The transition temperatures for the mixture were

I→A 69° C.

A→C* 50° C.

C*→K 8° C.

The response time at a voltage of ±30 and a temperature of 23° C. was 39μs. The response time at a voltage of ±40 and a temperature of 40° C.was 19 μs. The polarization at 23° C. was 39 nC/cm².

EXAMPLE 172

    ______________________________________                                        S-4-(4-methylhexyloxy)benzoic acid                                                                    30 wt. %                                              p'-(1,1-dihydroperfluorobutyloxy)-                                            phenyl ester (Compound 13)                                                    S-4-(4-methylhexyloxy)benzoic acid                                                                    20 wt. %                                              p'-(1,1-dihydroperfluorohexyloxy)-                                            phenyl ester (Compound 21)                                                    S-4-(2'-chloro-4'-methylpentanoyloxy)-                                                                20 wt. %                                              phenyl 4"-(1,1-dihydroperfluorobutoxy)-                                       benzoate (Compound 65)                                                        S-1,1-dihydroperfluorobutyl 4-[4'-(4''-                                                               30 wt. %                                              methylhexyloxy)benzoyloxy]benzoate                                            (Compound 70)                                                                 ______________________________________                                    

The transition temperatures for the mixture were

I→A 72° C.

A→C* 53° C.

C*→K 8° C.

The response time at a voltage of ±30 and a temperature of 26° C. was 59μs. The polarization at 26° C. was 37 nC/cm².

EXAMPLE 174

    ______________________________________                                        S-4-(1,1-dihydroperfluorohexyloxy)-                                                                   19 wt. %                                              thiolbenzoic acid p'-(4-methylhexyl-                                          oxy)phenyl ester (Compound 6)                                                 S-4-(4-methylhexyloxy)benzoic acid                                                                    20 wt. %                                              p'-(1,1-dihydroperfluorobutyloxy)-                                            phenyl ester (Compound 13)                                                    S-4-(4-methylhexyloxy)benzoic acid                                                                    23 wt. %                                              p'-(1,1-dihydroperfluorohexyloxy)-                                            phenyl ester (Compound 21)                                                    S-4-(2'-chloro-4'-methylpentanoyloxy)-                                                                19 wt. %                                              phenyl 4"-(1,1-dihydroperfluorobutoxy)-                                       benzoate (Compound 65)                                                        S-2-methylbutyl 4-(4'-octyloxybenzoyl-                                                                20 wt %                                               oxy)benzoate (Goodby and Leslie, supra)                                       ______________________________________                                    

The transition temperatures for the mixture were

I→A 81° C.

A→C* 58° C.

C*→K 23° C.

The response time at a voltage of ±30 and a temperature of 32° C. was 11μs. The polarization at a temperature of 32° C. was 30 nC/cm².

EXAMPLE 175

    ______________________________________                                        S-4-(4-methylhexyloxy)benzoic acid                                                                    50 wt. %                                              p'-(1,1-dihydroperfluorohexyloxy)-                                            phenyl ester (Compound 21)                                                    S-4-(2'-chloro-4'-methylpentanoyloxy)-                                                                50 wt. %                                              phenyl 4"-(1,1-dihydroperfluorobutoxy)-                                       benzoate (Compound 65)                                                        ______________________________________                                    

The transition temperatures for the mixture were

I→A 79° C.

A→C* 48° C.

The response time at a voltage of ±40 and a temperature of 42° C. was 12μs. The polarization at 42° C. was 75.5 nC/cm².

The various modifications and alterations of this invention will beapparent to those skilled in the art without departing from the scopeand spirit of this invention and this invention should not be restrictedto that set forth herein for illustrative purposes.

What is claimed is:
 1. A compound represented by the formula ##STR95##wherein z is 1 to 20, z' is 1 to 20, and y is 1to
 20. 2. A compound ofclaim 1 comprising 4-(1,1-dihydroperfluorohexyloxy)phenol.
 3. A compoundof claim 1 comprising 4-(1,1-dihydroperfluorobutyloxy)phenol.
 4. Acompound of claim 1 comprising 4-(1,1-dihydroperfluorooctyloxy)phenol.5. A compound of claim 1 comprising4-(1,1,2,2-tetrahydroperfluorohexyloxy)phenol.
 6. A compound of claim 1comprising 4-(1,1,7-trihydroperfluoroheptyloxy)phenol.